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PubMed2006

A solid-phase microextraction chamber method for analysis of manure volatiles.

Odors from livestock operations are a complex mixture of volatile carbon, sulfur, and nitrogen compounds. Currently, detailed volatiles analysis is both time consuming and requires specialized equipment and methods. This work describes a new method that utilizes a dynamic flux chamber, solid-phase microextraction (SPME), and gas chromatography-mass spectroscopy (GC-MS) to describe and compare the odorous compounds emitted from cattle and swine feces. Evaluation of method parameters produced a protocol for comparing relative emissions based on fixed sample temperature (20 degrees C) and exposed surface area (approximately 523 cm(2)), air flow rates (1 L min(-1) or 16 cm s(-1)), SPME exposure time (5 min), and chamber cleaning procedures (70% ethanol rinse and drying for 30 min at 105 degrees C) to minimize cross-contamination between samples. A variety of volatile organic compounds (VOCs) including alcohols, volatile fatty acids, aromatic ring compounds, ketones, esters, and sulfides were routinely detected and the relative emissions from fresh and incubated (37 degrees C overnight) swine and cattle feces were compared as a measure of potential to produce odorants during manure storage. Differences in the types and relative quantities of volatiles emitted were detected when animal species (cattle or swine), diet, fecal incubation, or sample storage conditions (20, 4, or -20 degrees C) were varied.

Animals↗
PubMedDate not supplied

Reactive airway disease in patients with prolonged exposure to industrial solvents.

This study examines the effects of volatile organic compounds (VOCs) at the workplace on pulmonary function tests. Forty-two patients with a history of industrial exposure to organic solvents and pulmonary symptomatology were studied. Lung function tests were determined utilizing screening spirometry lung volumes, diffusion capacity and methacholine stimulation test. While only 10-15% of the symptomatic patients had abnormal screening spirometry, 42% of the patients had significantly abnormal methacholine stimulation tests. These data show that exposure to volatile organic solvents is associated with bronchial hyperreactivity not commonly detected by screening spirometry and requires methacholine stimulation testing in individuals with unexplained symptomatology and history of exposure to industrial solvents. These findings indicate that the incidence of bronchial hyperreactivity is underestimated in patients with (1) verifiable exposure history to volatile organic compounds known to be pulmonary irritants, (2) pulmonary symptomatology with normal screening spirometry.

Adult↗
PubMed2005

Occupational hygiene in a Finnish drum composting plant.

Bioaerosols (microbes, dust and endotoxins) and volatile organic compounds (VOCs) were determined in the working air of a drum composting plant treating source-separated catering waste. Different composting activities at the Oulu drum composting plant take place in their own units separated by modular design and constructions. Important implication of this is that the control room is a relatively clean working environment and the risk of exposure to harmful factors is low. However, the number of viable airborne microbes was high both in the biowaste receiving hall and in the drum composting hall. The concentration (geometric average) of total microbes was 21.8 million pcs/m3 in the biowaste receiving hall, 13.9 million pcs/m3 in the drum composting hall, and just 1.4 million pcs/m3 in the control room. Endotoxin concentrations were high in the biowaste receiving hall and in the drum composting hall. The average (arithmetic) endotoxin concentration was over the threshold value of 200 EU/m3 in both measurement locations. In all working areas, the average (arithmetic) dust concentrations were in a low range of 0.6-0.7 mg/m3, being below the Finnish threshold value of 5 mg/m3. In the receiving hall and drum composting hall, the concentrations of airborne microbes and endotoxins may rise to levels hazardous to health during prolonged exposure. It is advisable to use a respirator mask (class P3) in these areas. Detected volatile organic compounds were typical compounds of composting plants: carboxylic acids and their esters, alcohols, ketones, aldehydes, and terpenes. Concentrations of VOCs were much lower than the Finnish threshold limit values (Finnish TLVs), many of the quantified compounds exceeded their threshold odour concentrations (TOCs). Primary health effects due VOCs were not presumable at these concentrations but unpleasant odours may cause secondary symptoms such as nausea and hypersensitivity reactions. This situation is typical of composting plants where the workers are exposed to dozens of VOCs simultaneously. The odour units (OU/m3) were measured using olfactometer. The numbers were 23,000 OU/m3 at the output end of the composting drum and 6300 OU/m3 in the exhaust pipe. Inside the composting hall, the number of odour units was 500 and 560 OU/m3.

Aerosols↗
PubMed2005

Novel insight into VOC removal performance of photocatalytic oxidation reactors.

UNLABELLED: A general model has been developed for analyzing the removal of volatile organic compounds (VOCs) by photocatalytic oxidation (PCO) reactors, taking into consideration of the photocatalytic (surface) reaction and the convective mass transfer coefficients including allowance for their spatial dependence. On this basis, a novel insight into VOC removal performance of PCO reactors is presented. The key parameter for evaluating PCO reactor VOC removal performance is the number of the mass transfer unit (NTU(m)), which is shown to be a simple linear product of three dimensionless parameters: the ratio of the reaction area to the cross-sectional area of the flow channel (A*), the Stanton number of mass transfer (St(m)), and the reaction effectiveness (eta). The A* represents the geometric and structural characteristic of a PCO reactor. The St(m) shows the synergistic degree of alignment between the fluid and mass flow fields, and reflects the convective mass transfer rate of the reactor. The eta, describes the relative intensity between the PCO reaction rate and the mass transfer rate. By using the relationship and the parameters, the influence of various factors on the VOC removal performance, the bottleneck for improving the performance and design of a PCO reactor can be determined. Three examples are used to illustrate the application of our proposed model. It is found that the VOC removal bottleneck is the reaction rate for honeycomb type reactor, while mass transfer rate for light-in-tube type reactor. With six fins the fractional conversion of a light-in-tube reactor increases about 70% relative to the one without any fins. PRACTICAL IMPLICATIONS: Indoor air quality problem caused by volatile organic compounds (VOCs) have annoyed people for many years. Photocatalytic oxidation (PCO) appears to be a promising technique for destroying VOCs in indoor air. With the model and the novel insight presented in this paper, the influence of various factors on the VOC removal performance can be determined. And the bottleneck for improving the performance of a PCO reactor can be easily identified. These are helpful for designing high performance PCO reactors and optimizing their operative performance.

Air Pollution, Indoor↗
PubMed2002

Direct evidence of atmospheric secondary organic aerosol formation in forest atmosphere through heteromolecular nucleation.

Atmospheric aerosols play a central role in climate and atmospheric chemistry. Organic matter frequently composes aerosol major fraction over continental areas. Reactions of natural volatile organic compounds, with atmospheric oxidants, are a key formation pathway of fine particles. The gas and particle atmospheric concentration of organic compounds directly emitted from conifer leaf epicuticular wax and of those formed through the photooxidation of alpha- and beta-pinene were simultaneously collected and measured in a conifer forest by using elaborated sampling and GC/ MS techniques. The saturation concentrations of acidic and carbonyl photooxidation products were estimated, by taking into consideration primary gas- and particle-phase organic species. Primary organic aerosol components represented an important fraction of the atmospheric gas-phase organic content Consequently, saturation concentrations of photooxidation products have been lowered facilitating new particle formation between molecules of photooxidation products and semi-volatile organic compounds. From the measured concentrations of the above-mentioned compounds, saturation concentrations (Csat,i) of alpha- and beta-pinene photooxidation products were calculated for nonideal conditions using a previously developed absorptive model. The results of these calculations indicated that primarily emitted organic species and ambient temperature play a crucial role in secondary organic aerosol formation.

Aerosols↗
PubMed2005

Separation and preconcentration phenomena in internally heated poly(dimethylsilicone) capillaries: preliminary modelling and demonstration studies.

The concept of achieving low-resolution separations in internally heated capillary membranes is discussed in terms of controlling the diffusion coefficients of volatile organic compounds in poly(dimethylsilicone) membranes in space and time. The behaviour of 1,1,1-trichloroethane in polydimethylsilicone was used in conjunction with a mixed-physics finite element model, incorporating second order partial differential equations, to describe time and spatial variations of mass-flux, membrane temperature and diffusion coefficients. The model, coded with Femlab, predicted highly non-linear diffusion coefficient profiles resulting from temperature programming a 500 [micro sign]m thick membrane, with an increase in the diffusion coefficient of approximately 30% in the last 30% of the membrane thickness. Simulations of sampling hypothetical analytes, with disparate temperature dependent diffusion coefficient relationships, predicted distinct thermal desorption profiles with selectivities that reflected the extent of diffusion through the membrane. The predicted desorption profiles of these analytes also indicated that low resolution separations were possible. An internally heated poly(dimethylsilicone) capillary membrane was constructed from a 10 cm long, 1.5 mm od capillary with 0.5 mm thick walls. Thirteen aqueous standards of volatile organic compounds of environmental significance were studied, and low-resolution separations were indicated, with temperature programming of the membrane enabling desorption profiles to be differentiated. Further, analytically useful relationships in the [micro sign]g cm(-3) concentration range were demonstrated with correlation coefficients >0.96 observed for linear regressions of desorption profile intensities to analyte concentrations.

Journal Article↗
PubMed2003

Changes in tropospheric composition and air quality due to stratospheric ozone depletion.

Increased UV-B through stratospheric ozone depletion leads to an increased chemical activity in the lower atmosphere (the troposphere). The effect of stratospheric ozone depletion on tropospheric ozone is small (though significant) compared to the ozone generated anthropogenically in areas already experiencing air pollution. Modeling and experimental studies suggest that the impacts of stratospheric ozone depletion on tropospheric ozone are different at different altitudes and for different chemical regimes. As a result the increase in ozone due to stratospheric ozone depletion may be greater in polluted regions. Attributable effects on concentrations are expected only in regions where local emissions make minor contributions. The vertical distribution of NOx (NO + NO2), the emission of volatile organic compounds and the abundance of water vapor, are important influencing factors. The long-term nature of stratospheric ozone depletion means that even a small increase in tropospheric ozone concentration can have a significant impact on human health and the environment. Trifluoroacetic acid (TFA) and chlorodifluoroacetic acid (CDFA) are produced by the atmospheric degradation of hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs). TFA has been measured in rain, rivers, lakes, and oceans, the ultimate sink for these and related compounds. Significant anthropogenic sources of TFA other than degradation HCFCs and HFCs have been identified. Toxicity tests under field conditions indicate that the concentrations of TFA and CDFA currently produced by the atmospheric degradation of HFCs and HCFCs do not present a risk to human health and the environment. The impact of the interaction between ozone depletion and future climate change is complex and a significant area of current research. For air quality and tropospheric composition, a range of physical parameters such as temperature, cloudiness and atmospheric transport will modify the impact of UV-B. Changes in the chemical composition of the atmosphere including aerosols will also have an impact. For example, tropospheric OH is the 'cleaning' agent of the troposphere. While increased UV-B increases the OH concentration, increases in concentration of gases like methane, carbon monoxide and volatile organic compounds will act as sinks for OH in troposphere and hence change air quality and chemical composition in the troposphere. Also, changes in the aerosol content of the atmosphere resulting from global climate change may affect ozone photolysis rate coefficients and hence reduce or increase tropospheric ozone concentrations.

Acetates↗
PubMed2003

The use of isotopes to identify landfill gas effects on groundwater.

An evaluation of the source of volatile organic compounds in groundwater samples was performed at a landfill in southern California. The 3H (tritium) content of the water in leachate and water from the gas-collection system (condensed water and entrained water droplets) and the delta 13C and 14C content of the inorganic carbon in landfill gas CO2, leachate, and gas-collection system water were used to characterize the dissolved inorganic carbon (DIC) inside the landfill, while the same parameters were monitored in groundwater samples from affected monitoring wells and an unaffected well. Tritium levels from leachate and gas-collection system condensate ranged from approximately 2000 TU to over 4000 TU, orders of magnitude higher than unaffected groundwater. The average 14C content of DIC in the landfill pore-water samples was 121 pMC and the 14C content of unaffected groundwater DIC was 93 pMC, while the 14C content of the dissolved inorganic carbon in groundwater with VOC detections ranged from 105 to 119 pMC. The delta 13C of DIC in pore water was consistently above 0 per thousand and the delta 13C of unaffected groundwater DIC was -20.3 per thousand, while the delta 13C of DIC in affected groundwater samples was increased from -17.3 to -13.2 per thousand. The increases in both delta 13C and 14C in landfill gas-impacted groundwater DIC generally correlated with the number of volatile organic compounds detected and their concentrations. Based on the tritium and DIC 14C levels in leachate and water from the gas-collection system compared to those of unaffected water, significant increases in the tritium content of the water would be expected to accompany VOC detections and increases in delta 13C and 14C caused by landfill water. The results rule out landfill water as the VOC source, leaving landfill gas as the source. The identities and concentrations of the specific VOCs in affected groundwater samples varied among wells as well as between two leachate samples, ruling out the use of a VOC "fingerprint" for leachate or landfill gas to be compared to groundwater VOC concentrations.

Carbon Isotopes↗
PubMed2000

Sediment-air equilibrium partitioning of semi-volatile hydrophobic organic compounds part 2. Saturated vapor pressures, and the effects of sediment moisture content and temperature on the partitioning of polyaromatic hydrocarbons.

A gas saturation methodology was used to determine the sediment/air partition coefficient (K(SA)) for phenanthrene and dibenzofuran on a local sediment from the Campus Lake, Baton Rouge. The effects of sediment moisture content, air relative humidity and temperature on K(SA) for phenanthrene were ascertained. The saturated vapor pressures of the compounds were also measured. The sediment moisture content had a striking effect on K(SA); increasing sediment moisture content decreased K(SA). Temperature also had a dramatic effect on K(SA). The variation with temperature was used to evaluate the heats of adsorption on both 'dry' (< 0.8% by mass of water) and 'wet' (> 6% by mass of water) sediments. The heat of adsorption for phenanthrene normalized to unit molecular surface area indicated for the physically adsorbed organic compound was seven times smaller than that for a water molecule. The experimental value of K(SA) was used to test a proposed theoretical model. A good agreement was observed for both phenanthrene and dibenzofuran. The model can be extended to other compounds and sediment types for prediction of air emissions from exposed sediment and dredged materials.

Air Pollutants↗
PubMed2000

Anaerobic utilization of essential oils by denitrifying bacteria.

Plant volatile organic compounds are a major carbon source in nature. We studied the degradability of these substances by anaerobic microorganisms in enrichment cultures with representative essential oils as organic substrates and nitrate as electron acceptor. Lemon and pine needle oil supported microbial growth in the presence of pure oil, whereas parsley seed, camphor, sage, fennel, and mint oil supported growth only when the essential oils were dissolved in an overlying phase of 2,2,4,4,6,8,8-heptamethylnonane. Thyme oil did not support denitrification. Analyses of the microbially degraded oils revealed the disappearance of monoterpenes, of several monoterpenoids, and of methoxy-propenyl-benzenes, including apiole and myristicin. Most-probable-number determinations for denitrifying communities in sewage sludge and forest soil yielded 10(6) to 10(7) monoterpene-utilizing cells ml(-1), representing 0.7 to 100% of the total cultivable nitrate-reducing microorganisms. The utilization of essential oils together with the common occurrence of this metabolic trait are indications for an environmentally important, but currently unexplored anaerobic turnover of plant volatile organic compounds in soil.

Alcaligenes↗
PubMed2000

Modeling effects of moisture content and advection on odor causing VOCs volatilization from stored swine manure.

Two models for evaluating the contents and advection of manure moisture on odor causing volatile organic compounds (VOC-odor) volatilization from stored swine manure were studied for their ability to predict the volatilization rate (indoor air concentration) and cumulative exposure dose: a MJ-I model and a MJ-II model. Both models simulating depletion of source contaminant via volatilization and degradation based on an analytical model adapted from the behavior assessment model of Jury et al. In the MJ-I model, manure moisture movement was negligible, whereas in the MJ-II model, time-dependent indoor air concentrations was a function of constant manure moisture contents and steady-state moisture advection. Predicted indoor air concentrations and inhaled doses for the study VOC-odors of p-cresol, toluene, and p-xylene varied by up to two to three orders of magnitude depending on the manure moisture conditions. The sensitivity analysis of both models suggests that when manure moisture movement exists, simply MJ-I model is inherently not sufficient to represent a more generally volatilization process, which can even become stringent as moisture content increases. The conclusion illustrates how one needs to include a wide variety of manure moisture values in order to fully assess the complex volatilization mechanisms that are present in a real situation.

Air Pollution, Indoor↗
PubMed2004

Biodegradation kinetics of volatile hydrophobic organic compounds in cultures with variable fractional volumes.

An extension of the models developed by Guha and Jaffé (Biotechnol Bioeng [1996] 50:693-699) to describe the phenanthrene biodegradation kinetics for the cultures with variable fractional volumes is presented. Batch experiments were conducted with a culture capable of degrading the phenanthrene using a single culture vessel from which samples were withdrawn over time to monitor the disappearance of phenanthrene. For accurate measurement of phenanthrene concentrations, a sampling procedure designed for quantifying the sorption of phenanthrene onto glassware was also introduced. The Monod parameters were estimated by nonlinear regression analyses of simultaneous solutions to the substrate utilization/volatilization and Monod equations for growth of the cell mass. The results demonstrate that the models were able to be extended to phenanthrene-degrading cultures with variable fractional volumes. When the ratio between sampling volume and volume of the culture medium was relatively small, the parameters obtained were similar to those which would be obtained using constant fractional volumes of culture medium. It was also found that the model's fit to the phenanthrene disappearance data in this study were better than those obtained by Guha and Jaffé, implying that the sorption process of phenanthrene during the sampling period could significantly affect the measurement of phenanthrene concentrations. Failing to account for these losses led to less accurate measurements of substrate concentrations, which in turn resulted in a poor estimation of the parameters. The findings of this study reduce considerably the experimental work necessary in the estimation of Monod kinetic parameters for the purpose of modeling.

Biodegradation, Environmental↗
PubMed2002

Radiocarbon content of synthetic and natural semi-volatile halogenated organic compounds.

Some halogenated organic compounds, such as polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polybrominated diphenyl ethers (PBDEs), have been suggested to have natural sources but separating these compounds from their commercially synthesized counterparts is difficult. Molecular-level 14C analysis may be beneficial since most synthetic compounds are manufactured from petrochemicals (14C-free) and natural compounds should have "modern" or "contemporary" 14C levels. As a baseline study, we measured, for the first time, the 14C abundance in commercial PCB and PBDE mixtures, a number of organochlorine pesticides, as well as one natural product 2-(3',5'-dibromo-2'-methoxyphenoxy)-3,5-dibromoanisole. The latter compound was isolated from a marine sponge and is similar in structure to a PBDE. All of the synthetic compounds were 14C-free except for the pesticide toxaphene. which had a modern 14C abundance, as did the brominated natural compound. The result for toxaphene was not surprising since it was commercially synthesized by the chlorination of camphene derived from pine trees. These results suggest that measuring the 14C content of halogenated organic compounds may be quite useful in establishing whether organic compounds encountered in the environment have natural or synthetic origins (or both) provided that any synthetic counterparts derive from petrochemical feedstock.

Animals↗
PubMed2002

The application of thermal desorption GC/MS with simultaneous olfactory evaluation for the characterization and quantification of odor compounds from a dairy.

Few analytical methods exist that combine chemical and sensory analysis of odorous compounds in whole air. Volatile organic compounds were collected by sampling air downwind from a small dairy through sorbent tubes of Tenax TA and Carboxen 569. Samples were analyzed by thermal desorption into a cryotrap and subsequent gas chromatographic separation, followed by simultaneous olfactometry and mass spectrometry. Because compounds are concentrated during sampling, sensory analysis encountered compounds at a concentration 40 times that in air, making this a useful method for identifying trace compounds participating in odor. Twenty odorous and nonodorous compounds were identified and quantified, including straight-chain and aromatic hydrocarbons, chlorinated compounds, alcohols, ketones, aldehydes, and organic acids, at air concentrations of 0.55-320.20 microg/m(3). Compound peaks were characterized by odors ranging from offensive to pleasant, demonstrating the integrative nature of olfaction. This method could be useful in studying many kinds of odors in air.

Animals↗